Making nanocrystalline mesoporous spherical particles

ABSTRACT

Spherical particles of one or more elemental metals and elemental carbon are prepared from a precursor in the form of a metal oleate. The metal oleate precursor is dispersed in a liquid vehicle and aerosol droplets of the dispersed precursor are formed in a stream of an inert gas. The aerosol droplets are heated in the stream to decompose the oleate ligand portion of the precursor and form spherical particles that have a mesoporous nanocrystalline structure. The open mesopores of the spherical particles provide a high surface area for contact with fluids in many applications. For example, the mesopores can be infiltrated with a hydrogen absorbing material, such as magnesium hydride, in order to increase the hydrogen storage capacity of the particles.

This application is a division of U.S. patent application Ser. No.13/226,733, titled “Making Nanocrystalline Mesoporous SphericalParticles”, filed Sep. 7, 2011 which is a Continuation-in-Part of U.S.patent application Ser. No. 12/828,353, titled “Making NanostructuredPorous Hollow Spheres with Tunable Structure,” filed on Jul. 1, 2010,now U.S. Pat. No. 8,728,361. Both the co-pending parent application andissued patent are assigned to the assignees of this invention. Thecontents of both applications are incorporated herein by reference.

TECHNICAL FIELD

This invention pertains to methods of making spherical particles thatare a composite of one or more elemental metals and elemental carbon.The spherical particles are characterized by a mesoporousnanocrystalline structure consisting of three-dimensional networks ofmetal nanocrystals. An aerosol-assisted process is employed usingsolutions comprising metal oleate coordination complexes.

BACKGROUND OF THE INVENTION

The above identified U.S. Pat. No. 8,728,361 discloses methods of makinghollow spherical particles that are a composite of one or more elementalmetals and elemental carbon. To make the hollow spherical particles, adispersion of a precursor material in a liquid vehicle is formed andcomprises at least one of (i) ions of the one or more metal elements andan organic ligand and (ii) a metal-organic ligand compound of each ofthe one or more metal elements. An aerosol of the liquid-dispersedprecursor material is formed in a stream of inert gas, which is thenheated to remove the liquid, decompose organic acid material and formporous, hollow spherical particles of a composite of the one or moremetals and carbon.

FIGS. 3A-3C, 4A-4B, 5 and 6A-6B of the prior application (Ser. No.12/828,353) are TEM images and depict hollow metal-carbon compositespheres that were formed from the as-disclosed aerosol-forming andthermal degradation process. As shown in these figures, the morphologyof the particles is characterized by a densely porous metal-carbonexterior shell in the shape of a sphere that has a less-dense porousinterior, such that the particles are characterized as “hollow.” Theparticles are characterized as hollow because of the less-dense porousinterior within the highly dense spherical shell. The hollow sphericalparticles are typically smaller than one micron in diameter and havenanometer-sized pores in their interior.

As discussed in our co-pending application, very small porous particleshave use in a wide variety of applications, such as, optical,electronic, magnetic, catalytic, and sensing devices ranging fromphotonic crystals to drug-delivery carriers. In certain applications,these porous spherical particles may be more advantageous than theirbulk materials because their porous structure, which results in lowerdensity, higher surface area, extra interior reaction space, and areduced amount of material.

SUMMARY OF THE INVENTION

Now, it is found that spherical metal-carbon or metal alloy-carboncomposite particles having a similar but different morphologicalcharacter can be formed from some of the same precursor materials and asimilar aerosol-forming and thermal degradation process. As before,composite particles of one or more elemental metals and elemental carbonare made from a precursor in the form of a coordination complex. But, inthis instance, the resulting structure of the particles is different.The particles of the present application have a generally uniform,mesoporous cross-section that does not have a densely porous exteriorshell, unlike the particles disclosed in our co-pending application.

The spherical particles of the present application also have use in awide variety of applications due to their porosity and high surfacearea, for example in catalysis. Further, it is now found that themeso-porosity of these spherical particles allows for the effectiveabsorption and release of hydrogen. In addition, the open mesoporesenable the particles to be infiltrated with additional hydrogenabsorbing materials, such as magnesium hydride.

As discussed in our U.S. Pat. No. 8,728,361, the morphology of theultimate spherical particles can vary depending on the materials used toprepare the metal-organic ligand precursors. Specifically, it is foundthat the morphology of the spherical particles varies depending on thethermal degradation behavior of the metal-organic ligand precursors,which is a function of the reactivity between metal compound and theorganic ligand as well as the thermal degradation behavior of theorganic ligand. The stronger the bond between the metal and the organicligand, the more likely it is that spherical particles will form with ahollow structure. When organic ligands with low thermal degradationtemperatures are used, the chances of forming hollow spherical particlesincreases.

The degree of ionization of the prepared metal oleate precursors canalso be controlled in order to direct the morphology of the sphericalparticles. Precursors with a high ionization degree, or a high number ofunbound inorganic ions, will result in the formation of hollow sphericalparticles, such as the particles disclosed in our U.S. Pat. No.8,728,361. On the other hand, precursors prepared according toembodiments of the present invention have a relatively low ionizationdegree, and lead to the formation of spherical particles that do nothave a densely porous exterior shell.

According to embodiments of the present invention, a precursor in theform of one or more metal oleates is prepared by reacting one or moremetal oxides, metal acetates, or metal acetylacetonates with oleic acidand heating the mixture to evaporate water, acetic acid oracetylacetone. The precursor may alternatively be formed by complexingmetal salts, such as metal chlorides or metal nitrates, with oleic acidin a basic solution, precipitating the precursor from the solution, andthen separating the precursor from any by-products.

As before, the prepared precursor is then dispersed in a suitablesolvent having a molar concentration of about 0.01 to about 0.5 mole ofmetal oleate per liter of dispersant. And metal-carbon compositeparticles are formed from the prepared precursor dispersion using anaerosol-forming and thermal degradation process. But, unlike our U.S.Pat. No. 8,728,361, use of a metal oleate precursor prepared accordingto embodiments of the present application results in the formation ofspherical particles that have a generally uniform cross-section and amesoporous nanocrystalline structure.

In practice, aerosol droplets of the liquid-dispersed metal oleateprecursor are carried through a heated tubular reactor in a stream of aninert gas. In preferred embodiments, the tubular reactor is heated toabout 550° C. and is operated at a volumetric flow rate of about 2.6L/min (STP). This configuration provides a suitable residence time forthe aerosol droplets in the reactor and allows for the relatively slowevolution of the mesoporous nanocrystalline structure of the sphericalparticles. A suitable temperature and residence time of the aerosoldroplets in the reactor will allow the organic ligands to decompose andthree-dimensional (3-D) networks of metal nanocrystals to form withinthe spherical particles, without contributing to the nucleation of metalions or atoms on the surface of the aerosol droplets.

Without intending to be limited by a proposed understanding of particleformation, it is believed that the nanocrystalline structure of thespherical particles is a result of a sequence of steps that occur whenthe aerosol droplets are heated. It is believed that the sequenceconsists of the: (1) formation of metal nanocrystals that are stabilizedby the oleate ligands which act as surface-capping agents at hightemperature, (2) formation of clusters of the metal nanocrystals, (3)fusion of the metal nanocrystals, and (4) formation of 3-D networks ofmetal nanocrystals within the aerosol droplets. The metal nanocrystalsare uniformly attached by fine elemental carbon particles. The carbonparticles exist as a residue from the decomposed organic ligands.

The spherical particles of the present invention are typically less thanone micron in diameter. The metal nanocrystals within the particlesrange in size from about 3 to 4 nanometers. The open passages betweenthe metal nanocrystals elemental metal form, opposed to metal oxideform. The low oxygen content and of the 3-D networks define mesopores,and have an average diameter centered at about 3 to 4 nanometers. Thenano crystalline mesoporous structure of the spherical particles resultsin a high surface-area of about 200 to about 250 m²/g.

The composition of the as-synthesized spherical particles consists of,by weight, about 80% one or more elemental metals, 18% elemental carbon,and 2% oxygen. Although the particles contain some oxygen, the particlesare in the reducing atmosphere produced in the tubular reactor enablesthe formation of the elemental metal particles.

In further embodiments, the hydrogen storage capacity of the sphericalparticles can be increased by infiltrating the open mesopores of theas-synthesized particles with particles of a suitable hydrogen storagematerial. For example, magnesium hydride (MgH₂) compounds, which areknown for their reversible hydrogen storage abilities, can be formed inthe mesopores of the as-synthesized spherical particles. MesoporousMgH₂-containing particles are prepared by immersing the as-synthesizedparticles in a dibutylmagnesium (Mg(Bu)₂) solution to form particlescontaining Mg(Bu)₂ compounds. The Mg(Bu)₂ precursor compounds are thenconverted to MgH₂ by heating the Mg(Bu)₂-containing particles to about200° C. under a hydrogen pressure of about 50 bar.

Spherical metal-carbon composite particles produced by this process maybe observed and characterized using electron microscopy, x-raydiffraction, spectroscopic analysis, electron tomography, nitrogenabsorption data, hydrogen adsorption data and the like.

Other objects and advantages of this invention will be apparent from afurther description of preferred (but not-limiting) embodiments of theinvention. The described practices are chosen to illustrate certainembodiments of this invention, and are not limitations on the scope ofthis invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of an apparatus for forming anaerosol in an inert gas stream from a liquid-dispersed metal oleateprecursor in an illustrative practice of this invention. The aerosol iscarried through a tubular reactor maintained at an elevated temperatureto decompose the organic ligands and solvent molecules, leavingmesoporous spherical particles having a nanocrystalline structure. Theparticles are then filtered from the stream, collected and post-heated.

FIGS. 2A-2B are transmission electron microscope (TEM) images ofmesoporous spherical particles formed according to embodiments of thepresent invention, which reveal the nanocrystalline network structure ofthe particles. FIG. 2A shows spherical particles of nickel, and FIG. 2Bshows spherical particles of an alloy of nickel and platinum. Thescale-bars in the respective figures represent fifty nanometers inlength.

FIGS. 3A-3C are slices of a three-dimensional image (tomogram) of asingle spherical nickel particle that was produced using electrontomography (ET) and a transmission electron microscope (TEM) operated at200 kV. To obtain the tomogram, several particles were deposited onto agrid and were tilted and imaged in a range from −70° to +70°. The tiltseries was aligned and used to reconstruct a three-dimensionalrepresentation of each particle. The reconstructions were furthersegmented to illustrate the relationship between nickel and carbon, andthe pores within the particles. FIGS. 3A-3C depict an array of images ofslices through the 3-D tomogram that have different thicknesses and showthe density variation between the Ni framework and the surroundingcarbon layer, as well as the 3-D nanocrystalline structure of theparticles. FIG. 3A depicts the density of the carbon particles and FIG.3B depicts the density of the nickel particles throughout the mesoporousnanocrystalline spherical particles. FIG. 3C shows the density variationof between the carbon and nickel particles throughout the sphericalparticles formed according to embodiments of the present invention. Thescale-bar represents twenty nanometers in length.

FIG. 4A-4E are transmission electron microscope (TEM) images of aerosoldroplets taken at different spaces times (τ), or residence times, withinthe tubular reactor. FIGS. 4A-4E are images of aerosol droplets thatwere taken at about τ equal to 0.6, 1.2, 1.8, 2.4 and 9.0 seconds,respectively, in the tubular reactor, and show the structural evolutionof the spherical particles. The scale-bars in the respective figuresrepresent fifty nanometers in length.

FIG. 5 is a bar chart comparing the percentage, by weight, of H₂adsorbed by four nickel-containing particles at 298 K and 1 bar. Thefirst bar on the chart, labeled Ni (NP), represents the average wt. % H₂adsorbed by commercially-available nickel nanoparticles having averageof 30 to 50 nanometers. The remaining bars on the chart represent thewt. % H₂ adsorbed by three types of spherical particles synthesizedaccording to preferred embodiments of this invention: Ni,Ni_(0.75)Pt_(0.25) and Pt. The Ni bar represents the average wt. % H₂adsorbed by nickel-carbon composite particles. The Ni_(0.75)Pt_(0.25)bar represents the average wt. % H₂ adsorbed by alloyed nickel-platinumand carbon composite particles, the metal nanocrystals comprisingapproximately 75 mol % nickel and 25 mol % platinum. The Pt barrepresents the average wt. % H₂ adsorbed by platinum-carbon compositeparticles.

DESCRIPTION OF PREFERRED EMBODIMENTS

It is found that very small spherical metal-carbon or metal alloy-carbonparticles having a nanocrystalline structure can be formed using anaerosol process. The spherical particles are typically less than onemicron in diameter and have an internal structure that primarilyconsists of 3-D networks of nanocrystals, such that the particles arecharacterized as mesoporous.

In general, one or more elemental metals are identified for preparationin order to form the mesoporous spherical particles. The prepared metalcompounds are then combined with oleic acid to form a dissolved metaloleate coordination complex. The coordination complex may be formed orplaced in a liquid medium, such as a solvent of tetrahydrofuran (THF).In the following paragraphs of the specification, metal-carbon and metalalloy-carbon particle forming methods involving the use of nickel orplatinum or mixtures of nickel and platinum will be presented asnon-limiting illustrations of the invention. Spherical particles ofnickel and platinum are candidates for catalyst applications in manydifferent products, and in other applications for small conductiveparticles with large surface areas. But practices of the invention areapplicable to metals generally and not limited to nickel and platinum.

FIG. 1 is a schematic drawing, partly in cross-section, illustrating theuse of a commercial laboratory size atomizer 10 (Model 3076, TSI, Inc.St. Paul, Minn.) operated with nitrogen as a carrier/atomization gas.This atomizer produces aerosol droplets with a size distributioncharacterized by a geometric standard deviation of 2 (95% of the liquidparticles have diameters between 0.25 and 4 times the mean diameter).

A precursor solution 12 of one or more metal oleates (as described abovein this specification) is placed in a suitable container or reservoir14. A vertically-oriented draw tube 16 provides a passage for a streamof the precursor solution 12 from its reservoir 14 to pinhole 18, anopening into atomization gas inlet 20 in the atomizer body 22. A streamof nitrogen gas (or other suitable atomization gas), indicated bydirectional arrow 24 is introduced into atomization gas inlet 20,reducing the pressure at pinhole 18. In an illustrative operation ofatomizer 10, nitrogen gas under an initial pressure of 40 psig wasintroduced under laminar flow condition through inlet 20 into theatomizer body 22 at a flow rate of 2.6 L (STP)/min. This nitrogen gasflow produced a pressure drop at pin hole 18, permitting the atmosphericpressure acting on the solution 12 to push a stream of the precursorsolution up through the draw tube 16 to pinhole 18. The precursorsolution entering the atomization stream 24 is converted to very smallaerosol droplets 26 (schematically enlarged in FIG. 1). As stated above,the aerosol droplets vary in size. Some of the larger droplets 28 fallback into the precursor solution 12. But, many of the aerosol droplets26 are carried in the flow of atomization gas 24. This combined streamof nitrogen gas and aerosol droplets 26 leaves the atomizer body 22 viaa tubular passage 32 and is now indicated as a combined stream 30 inFIG. 1. The continually-flowing combined stream 30 now also containsvaporized solvent from the precursor solution 12.

The combined stream 30 enters the inlet end of a one-inchinside-diameter, round glass/quartz/ceramic tube 34 which is enclosed inan electrical resistance heated tubular reactor or furnace 36. Thefurnace 36 is controlled to heat the glass/quartz/ceramic tube 34 andthe combined stream 30 to about 550° C. The residence time of theflowing combined stream 30 in the tube 34 is suitable for the heat tocause substantially complete degradation of the oleate ligand materialin the combined stream 30 and to allow for the structural evolution of3-D networks of metal nanocrystals within the aerosol droplets. Combinedstream 30 now contains polydisperse mesoporous spherical metal or metalalloy particles (with some residual carbon) 42, degradation productsfrom the ligand material and solvents, as well as the nitrogenatomization gas. Combined stream 30 exits the glass/quartz/ceramic tube34 through passage 38 and is directed through a filter 40. The filter 40is heated and maintained, for example, at about 80° C. It collects thespherical metal particles 42 while permitting the exhaust stream 46 ofnitrogen and ligand degradation products through outlet passage 44.

The now-fabricated, spherical metal particles are post-heated, forexample at about 550° C. for 30 minutes in a nitrogen atmosphere, toremove or carbonize any remaining organic substances.

It is believed that the structural evolution of the spherical particlesresults from the formation of metal nanocrystals within the aerosoldroplets and their fusion into 3-D networks within the heated zone. And,in order to complete the formation process, a suitable residence time(space-time) τ of the aerosol droplets in the heated zone is about 3 to10 seconds, and, preferably, at least nine seconds.

Without intending to be limited by a proposed understanding of particleformation, it is further believed that the formation of the metalspherical particles involves the following sequential steps. First,aerosol droplets are formed containing the precursor solution, which arethen carried by a nitrogen stream into the heated tube furnace where thesolvent starts to evaporate. Metal nanocrystals begin to form in theaerosol droplets from the metal ions or atoms and are stabilized by theoleate ligands, which act as capping agents. The metal nanocrystalscontinue to form into clusters of nanocrystals, and much of the organicmaterial is expelled from the aerosol droplets, but some carbon mayremain. Finally, the aerosol droplets are primarily filled with metalnanocrystals that are organized into a spongy 3-D network skeleton. Themetal nanocrystals are uniformly attached by fine carbon particles.

However understood, this aerosol process and suitable variations permitthe atomization and aerosol formation of the metal oleate precursormaterial and its processing into spherical metal-carbon or metalalloy-carbon composite particles.

EXAMPLES

Mesoporous spherical particles are formed from a solution comprising aprecursor of one or more metal oleate coordination complexes. Ingeneral, the metal oleate precursors are formed by complexing one ormore metal-containing compounds with oleic acid. In preferredembodiments, the precursor is prepared by reacting metal oxides,acetates or acetylacetonates with oleic acid under heating byevaporation of water, acetic acid, or acetylacetone. In furtherembodiments, the metal oleate precursor is prepared by complexing metalsalts, such as metal chlorides or metal nitrates, with oleic acid underbasic condition in solution. Precursors prepared according to thefollowing illustrative examples have a relatively low ionization degree,and lead to the formation of spherical particles that do not have adensely porous exterior shell.

The prepared metal oleates are dispersed in a liquid medium of, forexample a solvent of tetrahydrofuran (THF), before they are atomizedinto aerosol droplets using a commercial atomizer. The preferredconcentration of the metal oleate dispersion depends upon the solubilityof the metal oleate in the solvent. For example, when nickel (II) oleateor platinum (IV) oleate is dispersed in a solvent of THF, a suitablemolar concentration of the solution is about 0.01 to about 0.5 moles ofnickel or platinum oleate per liter of THF.

THF is a very useful solvent for dispersing the metal oleate precursorsbecause it is liquid at ambient temperatures, readily forms aerosols ofthe complexes and easily vaporizes during thermal degradation of thecomplexes. THF displays moderate polarity.

The following experimental examples of these practices are illustratedwith respect to the preparation of nickel and platinum containingprecursors. But the practices are not limited to these metals. They aregenerally applicable to any elemental metals from which it is desired toproduce mesoporous spherical carbon-metal particles.

Example 1

Nickel (II) oleate is prepared by mixing 2.48 g of nickel acetate and5.64 g of oleic acid with stirring for about one hour. The mixture isheated to about 150° C. to evaporate the acetic acid and form atransparent liquid of nickel (II) oleate. Nickel (II) oleate can also beprepared by mixing 2.57 g of nickel acetylacetonate and 5.64 g of oleicacid with stirring. The mixture is then heated to evaporate theacetylacetonate and form a transparent liquid of nickel (II) oleate.

In this example, 1 g of the prepared nickel (II) oleate precursor isadded to 100 mL of THF. However, up to about 20 g of the prepared nickeloleate precursor can be added to 100 mL of THF to form the precursordispersion.

The nickel oleate-THF precursor dispersion is then atomized into aerosoldroplets using a commercial atomizer (Model 3076, TSI, Inc.) withnitrogen as a carrier/atomization gas. The aerosol droplets are passedthrough a tubular reactor that is heated to about 550° C. where theaerosol droplets are converted to spherical particles. The sphericalparticles are subsequently collected by a filter.

The tubular reactor is preferably operated at a volumetric flow rate ofabout 2.6 L/min (STP). The geometry of the tubular reactor within theheating zone is about 1″ (ID)×30″ (L). The as-synthesized particles arethen post heated at about 550° C. under nitrogen gas for about 30minutes.

FIG. 2A is a transmission electron microscope (TEM) image of sphericalnickel particles that were formed using the nickel (II) oleate precursoras prepared above in this example. The TEM image reveals thenanocrystalline network structure of the spherical nickel particles.

Particles synthesized by this process can be characterized using XRD(Panalytical X'Pert Pro X-ray diffractometer, Cu Kα), TEM (FEI, CM-120,accelerating voltage 120 kV), STEM and chemical mapping (FEI Titan, FEGTEM/STEM System, accelerating voltage 300 kV), and SEM (JEOL JSM-6700F).Electron tomography can be performed with a FEI Tecnai F20 operated at200 kV. To construct a tomogram of the as-synthesized sphericalparticles, several particles are deposited onto a grid and are tiltedand imaged in a range from −70° to +70°. The tilt series are thenaligned and used to reconstruct a three-dimensional representation ofeach particle. The reconstructions can be further segmented toillustrate the relationship between nickel and carbon throughout theparticles. XPS spectra can be collected with a PHI 3057 spectrometerusing Mg Kα X-rays at 1286.6 eV and Al Kα radiations at 1486.6 eV.Nitrogen adsorption experiments are performed at 77 K and low pressure.

The chemical composition of the spherical particles is determined usingenergy-dispersive spectroscopy (EDS). The results suggest that theparticles contain about 80, 18, and 2 wt-% nickel, carbon, and oxygen,respectively. STEM-EDS mapping analysis of a single particle revealsthat the particles contain a homogeneous distribution of nickel andcarbon throughout the particle. Electron tomography is performed toobtain a 3-D reconstruction of the spherical particles and theirinternal nanocrystalline structure. It is found that the metalnanocrystals are primarily organized into a spongy 3-D network skeleton,and are uniformly attached with fine carbon grains. Total volumereconstruction reveals that the metal nanocrystals develop into 3-Dnetworks, which is in harmony with the results obtained by TEM, STEM,and STEM-EDS. Consistent with the discovery of the 3-D networkstructure, nitrogen sorption shows a typical type IV isotherm.

The mesoporous spherical particles have a high surface area of about 211m²/g. The pore size distribution of the particles is calculated by theBarrett-Joynes-Halenda (BJH) method from the desorption branch, andshows a uniform diameter centered at about 3.5 nm. It is worthy to notethat the surface area of the particles attributed to the micropores iscalculated to be around 26 m²/g, which suggests that the majority of theparticle surface area can be attributed to the structure of themesopores. Due to the presence of carbon, the particles retain more than200 m²/g of surface area even after sintering at 550° C. for 6.5 hours,which is of particular importance for catalytic applications.

Example 2

The synthesis strategy of Example 1 may be further extended to makespherical composite particles of metal alloys and carbon. For example,binary spherical particles of a Ni_(x)Pt_((1-x)) alloy can be made fromnickel (II) oleate and platinum (IV) oleate precursors. And TEM and STEManalysis confirm that these metal alloy composite particles exhibit asimilar nanocrystalline structure to that of the nickel particlessynthesized in Example 1.

In this example, nickel (II) oleate is prepared by dissolving 1.30 g ofNiCl₂ in 100 mL of methanol, and then adding 5.5 mL oleic acid. 50 mL ofa 0.4 molar NaOH methanol solution is dropped into the NiCl₂-methanolsolution under magnetic stirring conditions for about one hour toprecipitate nickel (II) oleate from the solution. The green precipitateof Ni (II) oleate is extracted with hexane, and the solvents are thenremoved under vacuum overnight.

Platinum (IV) oleate is prepared by dissolving 2 g of platinumhydrochloride (H₂PtCl₆.6H₂O) in hexane, and adding 11 mL oleic acidunder magnetic stirring conditions at high temperature for about fourhours. The solvent is then removed under vacuum overnight.

In the following example, a dispersion of the nickel oleate and platinumoleate precursors is prepared by dissolving the precursors in THF. Tomake Ni₁₉Pt₁ alloy, 11.837 g of nickel (II) oleate and 1.323 g ofplatinum (IV) oleate are dissolved in 100 mL of THF at room temperatureto form a homogenous solution.

As before, the metal oleate precursor dispersion is atomized intoaerosol droplets using a commercial atomizer with nitrogen as acarrier/atomization gas. The aerosol droplets are passed through atubular reactor that is heated to about 550° C., where the aerosoldroplets are converted to spherical particles. The spherical particlesare subsequently collected by a filter.

FIG. 2B is a transmission electron microscope (TEM) images of sphericalNi_(0.5)Pt_(0.5) alloyed particles, which reveals the nanocrystallinenetwork structure of the particles.

Chemical mapping of the Ni_(x)Pt_((1-x)) alloy particles suggests thatthe particles contain a homogeneous distribution of Ni and Pt within thespheres. XRD of the Ni_(x)Pt_((1-x)) alloy particles reveals that theyexhibit a FCC structure, as the peaks shift to the lower 20 withincreasing Pt content. This result indicates that Pt replaces Ni in theformation of these alloys. Moreover, the unit cell parameters of thealloy agree well Vegard's law, a=a_(Ni)x+a_(Pt)(1-x), where a_(Ni) anda_(Pt) is the lattice parameter of Ni or Pt, respectively, and x is themolar fraction of Ni. This further confirms that the composition of thealloy particles can effectively be controlled. TernaryNi_(x)Pt_(y)Pd_((1-x-y)) alloy particles can also be successfullysynthesized by this method.

Example 3

In a further embodiment, the open mesopores of the as-synthesizedspherical particles are filled with another material, for example amaterial that is capable of storing and releasing hydrogen. In thisexample, the mesopores of spherical Ni—C particles are infiltrated witha solution of dibutylmagnesium (Mg(Bu)₂) as a precursor for introducingMgH₂ into the mesopores of the particles.

In this example 0.5 g of the as-synthesized spherical Ni particles areloaded in a Schlenk tube in a glovebox, which is evacuated to 500 mTorr.After evacuation, 10 ml of a 1 M Mg(Bu)₂ heptane solution is injectedinto the Schlenk tube to immerse the Ni particles for about 24 hours.Then, the Ni particles—now containing Mg(Bu)₂—are obtained using acentrifuge and are dried in glovebox. Finally, the Mg(Bu)₂ is convertedto MgH₂ by heating the particles to about 200° C. under a hydrogenpressure of 50 bar. Thus, the mesopores of the spherical Ni—C particlesnow contain very small particles of MgH₂.

Example 4

The hydrogen storage capacity of the as-synthesized spherical Niparticles can be evaluated using a Micromeritics ASAP 2020 at 298 K.Excess hydrogen sorption measurements may be performed at high pressuresusing a PCTPro-2000 (Hy-Energy Scientific Instruments) at 77 K and a GasReaction Controller (Advanced Materials Corporation), which is attachedto a chiller at 243 K, 276 K, 298 K, and 325 K.

As shown in FIG. 5, the hydrogen storage capacities of the spherical Niparticles at room temperature is calculated to be less than about onepercent, by weight, in spite of the high surface area of the Niparticles.

The hydrogen storage capacity of the spherical Ni particles is believedto be limited by NiH_(0.5) (0.84 wt. % at 3.45×10³ bar and 298 K), whichis low for practical application. But, the hydrogen storage capacity ofthe spherical metal particles can be increased by controlling thecomposition of the particles. For example, as shown in FIG. 5, sphericalNi_(0.75)Pt_(0.25) particles exhibit greater hydrogen storage capacitythan non-alloyed Ni particles.

Example 5

To understand sequential steps in the formation of the sphericalparticles, a glass tube, with the same dimension as that of the reactor,is wrapped with heating types to create a series length of the heatedzone (equivalent to a series of τ, or space time). Particles producedfrom these reactors are investigated by TEM, revealing the structuralevolution of the particles during this rapid continuous process. Asshown in FIGS. 4A-4E, TEM images of the particles collected at τ equalto 0.6, 1.2, 1.8, 2.4 and 9.0 seconds, respectively, reveal thesequential steps involved in the spherical particle formation. First,dispersed metal nanocrystals of nickel are formed at about τ=0.6 seconds(FIG. 4A). The metal nanocrystals are fused into nanocrystal clusters atabout τ=1.2 seconds (FIG. 4B), and 3-D networks of the metalnanocrystals appear at about τ=1.8 to 2.4 seconds (FIGS. 4C-4D). Furthersintering and decomposition of the organic ligands leads to theformation of spherical nickel particles at about τ=9.0 seconds (FIG.4E). The formation of metal nanocrystals can be attributed to thethermolysis of the metal oleate precursors and from the reducingatmosphere produced by the decomposition of the organic ligands and thesolvent molecules. Gas chromographical studies confirm the proposedmechanism, and the formation of CO, —CHO containing molecules and otherreducing species in the gaseous stream.

The specific embodiments of practices of the invention that have beendescribed are only for the purpose of illustration and not to beconstrued as limiting the scope of the invention.

1. A method of making spherical particles that are a composite of one ormore elemental metals, elemental carbon, and oxygen, the methodcomprising: forming a metal oleate precursor by reacting one or moreinorganic metal salts of the one or more elemental metals with oleicacid in a basic solution; precipitating the metal oleate precursor fromthe solution; separating the metal oleate precursor precipitate from anyby-products; forming a dispersion of the metal oleate precursor in asolvent of tetrahydrofuran; forming aerosol droplets of the dispersedprecursor in a stream of an inert gas; and heating the aerosol dropletsin the stream to evaporate the solvent, decompose organic material, andform spherical particles of the one or more elemental metals, elementalcarbon, and oxygen having a uniform mesoporous nanocrystallinestructure.
 2. The method of making spherical particles as recited inclaim 1 further comprising: heating the aerosol droplets in the streamfor a sufficient amount of time so that nanocrystals of the one or moreelemental metals form in the droplets, the decomposed organic materialis expelled from the droplets, and the metal nanocrystals becomeorganized into a three-dimensional network in which the nanocrystals areuniformly attached by fine elemental carbon particles.
 3. The method ofmaking spherical particles as recited in claim 1 wherein the one or moreinorganic metal salts are of a metal chloride or a metal nitrate.
 4. Themethod of making spherical particles as recited in claim 1 wherein theone or more elemental metals are at least one of nickel and platinum. 5.The method of making spherical particles as recited in claim 1 whereinthe aerosol droplets are heated to a temperature of about 550° C.
 6. Themethod of making spherical particles as recited in claim 1 wherein theaerosol droplets are heated to a temperature of about 550° C. in areducing atmosphere.
 7. The method of making spherical particles asrecited in claim 1 further comprising: immersing the spherical particlesin a solution of dibutylmagnesium; removing the particles from thesolution; and heating and pressurizing the particles in an atmosphere ofhydrogen gas to form magnesium hydride particles in mesopores of thespherical particles.
 8. The method of making spherical particles asrecited in claim 1 in which the composition of the metal oleateprecursor is selected such that the pores of the formed sphericalparticles are sized for absorption and release of hydrogen.
 9. A methodof making spherical particles that are a composite of one or moreelemental metals, elemental carbon, and oxygen, the method comprising:forming a metal oleate precursor by reacting one or more metal oxides,metal acetates, metal acetylacetonates, or inorganic metal salts of theone or more elemental metals with oleic acid; separating the metaloleate precursor from any by-products; forming a dispersion of the metaloleate precursor in a solvent of tetrahydrofuran; forming aerosoldroplets of the dispersed precursor in a stream of an inert gas; andheating the aerosol droplets in the stream to evaporate the solvent,decompose organic material, and form spherical particles of the one ormore elemental metals, elemental carbon, and oxygen having a uniformmesoporous nanocrystalline structure.
 10. The method of making sphericalparticles as recited in claim 9 in which the composition of the metaloleate precursor is selected such that the pores of the formed sphericalparticles are sized for absorption and release of hydrogen.